Compounded oil



2341,15? sr rEs PATENT OFFICE.

a 'oomwzo n. k I W i ft, panyorcalifornia, 8anI'ranclaoo,0allf.,aeorp poratlon of Delaware v 1 No Drawing. "Application January 13, r941, Q "sensmasvazso c V I 11 Claims. (Cl. 252-44) This invention relates to a new and useful comtional example of such utility comprises use as a position of -matter and involves a composition heat transi'er fluid where it may be desirable to comprising a hydrocarbon oil and a metal phenate inhibit or prevent the formation of a deposit on of a relatively high molecular weight phenol. the metal surface from or to which heat is being This application is a continuation-in-part of 5 conveyed. Y Y Y i r our parent application Serial No. 233,328, filed We have .also discovered that certain metal October 4, 1938, and is directed to a divisional asphenates have a combination of properties herepect of the invention disclosedin the parent case, tofore unknown and particularly desirable in a The production oi improved hydrocarbon oils, compounded mineraloil, namely,v the ability to and particularly of lubricating oils having desired impart resistance to deterioration by heat or the characteristics, has been the subject of extensive ability to inhibit piston ring sticking, freedom r a and investigation in r cent years, G nfrom the production of increased wear on cylinder erally speaking, the compounding of hydrocarbon walls and piston rings as compared-with uncomoils to obtain desired characteristics involves empounded mineral oils, and low corrosivity as replrlcal henomena, and the action of untested spects the chemical action of the compounded oil types of compounding agents cannot be predicted. a on bearing metals, such as cadmium-silver alloys.

A characteristic which has been the subject of Although various c mpounded mineral oils are extensive investigation is the tendency of hydro-, known w h are p ble of inhibiting Piston rin carbon oils to deteriorateor partially decompose sticking, the discovery of specific compounding when subjected to high temperatures. This deents p ble of imparting the above combina terioration is evidenced by the deposition of adi n o P p rties to hydrocarbon oils repr t hesive deposits on hot metallic surfaces over an unobvious and important disc e ywhich the hydrocarbon oil may flow. 'It is im- Metal phenates which may be added to hydroportant that resistance to such deterioration be carbon oils such as mineral lubricating oils to pro imparted to hydrocarbon oils, particularly to luvide' a new composition of matter of the type bricating oils, in order that such compositions may herein involved comprise the earth be relatively free from the tendency to form such nd other metal phenatesp ific examples of deposits even under high temperatures and severe Such metal phenates are! Sodium phenates, po-

operating conditions. .A direct result of this type t ss um phenates, beryllium phe tes. calcium of deterioration during lubrication of internal p n tes, Strontium p s. barium phenates. combustion engines, such as engines of the Diesel magnesium phenates. Z1110 phenates, adm u type, is the tendency of the oil to cause or permit phenates and aluminum phenates.

the sticking of piston rings; Compounds which The phenates are pref ly formed from high render hydrocarbon oils more resistant to demolecular w i t p e ols f th typ f rmula: terioration by heat at high temperature levels on usually, though not always, impart to the oil the u ability to inhibit piston ring sticking in internal combustion engines and permit longer periods of operation of such engines without the necessity of major overhauls heretofore occasioned by stuck piston rings. y in which it, vjw, a: and y are selected from the It has been discovered that dispersion of metal group consisting of hydrogen, hydrocarbon, on phenatesln hydrocarbon oils, such as mineral luand hydroxyl radicals. The phenol preferably bricatingoil, imparts new and unpredictable propcontains at least one alkyl group containing more erties to the composition. These new properties than four carbon atoms. However, it is to be unrender the compounded oil particularly useful for derstood that the broader aspects of the invention various purposes. For example, alkaline earth include other phenols which contain more than phenates like calcium a .lauryl phenate, calcium ten carbon atoms. The term hydrocarbon radicetyl phenata'barium ,cetyl phenate,- calcium di-' cal" is intended to include alkyl, aryl. aralkyl, amyl' phenate, calclumheptyl phenate and other alkaryl or cyclic'nonbenzenoid groups. The term metal phenates lik ejalurninum alkylphenat-es and oxy radical? refers toa group in which the hyalkali metal alkyl phenates impart to hydrocarbondrogenof an hydroxyl radical has been replaced compositions an increased resistance to deteriora-J by esterification, neutralizationor the like; Al

t n by'he'at and th sbi ityjt mmbitpiston ring though phenols containing at leastone alkyl substicking when usedas' acrankcas'e lubricant lain-i stituent are preferred, the invention does not pre ternal combustion'engines,'such as'Diesel engines. I elude compounds containing no alkyl groups and" In ge'neraLlt has been discoveredthat the new, embodies the substitution of .aryl, alkaryl, aralkyl compositions herein disclosed are more stable to and cyclic ncnbenzenoid groups in the-aromatic heat than is the hydrocarbonoil fromwhlch the nucleus to which the phenolic hydroxyl group is compositions are'compounded. The new composi 00 directly attached, i, e tions or this invention are therefore useful wher Eaamples of specific compounds which maybe ever resistance to-h'ea't is important. An addiutilized comprise sodium lauryl phenate, sodium cetyl phenate, calcium lauryl phenate. calcium cetyl phenate, calcium diamylphenate. calcium heptyl phenata. calcium p-tertiary-amyl phenatc. calcium mono-chloro-amyl phenate. calcium peyclohexyl phenate, aluminum lauryl phenate. aluminum dicetyl phenats, magnesium cetyl phenate. barium cetyl phenate. and calcium cetyl cresylate. These compounds are suilciently solubleinminerallubricatingoils thattheymaybe added thereto with advantage. as herein previously ted out.

'los i a thoaeskilledintheartintheprenaration of the compositions of this invention, the following specific examples are given:

An alkyl phenol desirable for present purposes may be prepared as follows:

Ipample L-Phenoi and a butane polymer having an apparent molecular weight of 194 and obtainedbypoiymerisationofamixtureofbutenes containing butane-1, butene-2. and isobutene were .mixed. To this mixture,eontaining 23'! grams of phenol and 500 grams of the above-mentioned butene polymers, 140 cubic centimeters of 94% sulfuric acid was added slowly with agitation. The temperature was kept below 85' 1''. during addition of the acid. The mixture was agitated for two hours after the addition of acid was completed and permitted to come to room temperature. The reaction product was then diluted with an equal volume of water and placed in a sealed autoclave where it was heated at 350' F. for an hour with. agitation. The product was washed with water, 5% sodium carbonate solution'and again with water in order to free it of sulfuric acid, sulfonates and unreacted phenol. A 93% yield of high molecular weisht'water-insoluble alkyl phenol having an acetyl number of 181 was obtained.

An additional example of a method of preparing alkyl phenols suitable for use in this invention comprises:

trample 2.'-51l grams ofcrude cresylic acid. mgr-ems of olefin polymerscontaining an average or 14 carbon atoms per molecule, and 475 grams of 88% sulfuric acid were utiliud in preparing an aikylated sresol. These ingredients were combined and treated in the manner described above for preparation of cetyl phenol. The product was vacuum-distilled at mm. and a 50 to 90% cut of an alkyl phenol obtained which had a molecular weight of 291 and was used to prepare the calcium salt hereinafter described in Example 6.

It is to be understood that the above examples are given by way of illustration only and that other condensation reactions utilizing alcohols. alkyl chlorides and the like ratherthan olefins may be adopted as a starting material for introducing the alkyl group into the aromatic nucleus.

Also, other known condensation agents. such as aluminum chloride. zinc chloride, etc., may be' utilized for effecting alkylation of the phenol. A mixture of sulfuric and glacial acetic acids may be used with advantage as a condensing agent. A suitable mixture comprises 100 parts by weight 98%Ba80ito topartsbyweightofglacial acetic acid. The presence of the acetic acid facilitates temperature control and gives a softer. easier handled reaction product.

The following comprise illustrative examples of methods of preparing the metal phenates of this invention from the alkyl phenols:

trample 3.447 grams of an alkylated phenol having an apparent molecularjweight of 347 were agitated for six hours at 500' I". with 64 grams of powdered calcium carbide. Algaseous reaction product containing'acetylene was formed and removed. 'The product remaining in thereaction zone was a dark-colored brittle solid at room temperature and comprised a calcium salt of the alkylated phenol. 94% of the theoretical yield of calcium alkvl phenate was obtained as shown by an analysis of a sample or the reaction product freed from calcium carbide by filtration of its petroleum ether solution.

trample 4.485 grams of an alkylated phenol having an apparent molecular weight of 290 were agitated for six hours at from approximately 500 I. to 540' I". with 90 gram of calcium carbide.

gas containing acetylene was formed and removed. The product in-the reaction zone was a dark-colored brittle solid at room 1 temperature. A

yield of calcium aikyl phenate. representing 96% of that theoretically possible, was obtained.

trample 5.44 grams of p-cyclohexyl phenol and 20 grams of powdered calcium carbide were heated together at 350' I". for one hour. The I product was a tan-colored powder insoluble in petroleum ether. soluble in benzene. and comprising the calcium salt of p-cyclohexylphenol.

E's-ample 62-234 grams of an alkyl cresol (molecular weight 291) and 25 grams of powdered calcium carbide were heated at 530 F. with stirring for four hours. The product obtained comprising the calcium salt of alkyl cresoi was a hard brittle solid. soluble in mineral oil.

It is believed that the reactions occurring in the above examples may be represented by the following equation: V,

CaCa-i-ZR-CsHrOH- CaHfl-CaMrHQ): Metal carbides other than calcium carbide give the above type reaction and may be utilized. Such other compounds comprise those metal carbides which are known to react with water to yield acetylene. These metal carbides are herein termed acetylides" and comprise the carbides of the alkali metals and the alkaline earth metals, namely.sodium, potassium, rubidium, cesium,lithium, magnesium, caicium, strontium and barium.

Additional examples of methods of preparing metal phenates 'useful in the compositions of this invention comprise the following:

Example 7. To 217 grams of an allryl phenol (molecular weight 290) was added 17.2 grams of sodium metal. The temperature was maintained at approximately 350' 1". and the sodium metal added in small pieces while the mixture was stirred mechanically. The evolution of hydrogen was quiet and the time for completion of the reaction was about three hours. At 300' F. the product was a viscous brown liquid. Mineral lubricating oil was added at this temperature to give a 1% solution of the compound.

Examples-100 grams of an alkyl phenol (molecular weight 290) and 15 grams of aluminum wire were heated together. A crystal of iodine was added as a catalyst. The reaction continued until no further hydrogen evolution The prod t was dissolved in petroleum ether. iiltered,. and the petroleum small increments to maintain a rapid but safe evolution of hydrogen. Before the enre q n ty or magnesium had been added, the ca hm ifi itifllocemmmi M cent 50 eaction mixture became too viscous to stir even ,5, an 611 at 000 1''. This mixture was dissolved in acid A!!! 21.! treated S. A. E. 30 Western lubricating oil and Y The o myl phenate was dissolved in an acid toppedto480l".at5mm.pressureinastill.

Example 10.'7.6 grams oi barium hydroxide were dissolved in '7 cc. of water at 212 F. To this was added, with agitation, about 5 grams of cetyl phenol and 7 cc. of ethyl alcohol to promote solution of the cetyl phenol and facilitate reaction. The mixture wasboiled for about three minutes, extracted with a hydrocarbon. thinner, the extract filtered and the thinner evaporated. The product obtained was an amber. brittle semisolid containing approximately 65% of the barium salt of cetyl phenol. The reaction product as obtained was dissolved as a 1% solution in lubricating oil and found by engine test to satisfactorily inhibit piston ring sticking.

To illustrate the preparation oi calcium chloramvl phenate and oils containing the same, the following is given:

Example 11.-82 grams or p-tertiary amylphenol was dissolved in 500 cc. 0! 50% alcohol. Chlorine was bubbled through the solution for ten minutes, keeping the solution out of the sunlight. A heavy oil precipitated and was drawn oil. The oil was dissolved in petroleum ether and washed several times with music: solution and with water. Solvent was removed on a steambath. Analysis:

Chlorine per cent-.. 21.32 Neutralization N0. 290

70 grams of this chlo'ramyl phenol was mixed with 22 grams Ca(OH): and 1 liter of a petroleum hydrocarbon thinner. This mix was refluxed at about 220 the water being collected, for four hours. The petroleum hydrocarbon solution'was filtered and gave 5-10 grams of an amber-colored semi-solid on removal of solvent. The residue from filtration was extracted with boiling benzene, and on removal of the benzene yielded about 45 grams of a white solid. Analysis of white solid 5 refined naphthenic base oil, 8. A. E. 30, and the wire, '7 grams. were heated together in the pres;

ence of a crystal at iodine. Unreacted phenol was distilled oil and the'phenate dissolved-in petroleum ether. This solution was filtered and solvent removed. The product was a hard brittle solid with the following analysis:-

(larb p cent 51.30. Hydrogen do 6.76 Ash do 20.2 25 l\io1e eular weigh 428 The proportion of metal phenates added .to

mineral lubricating oils may vary widely, de

pending upon the uses involved and the prop;- erties desired. As little as 0.1% by weight of the phenate gives measurable improvements, al-' though from approximately 0.25 to approximately 2% phenate is preferred where fhecompounded oil is to be used as a crankcase lubricant for internal combustion engines. As much as by weight of various of the phenates may be dissolved in mineral oil for the p rpo e of preparing a concentrate capable of dilution with lubricating oils and the like. Such concentrates comprise a convenient method of handling the phenates and maybe used as a compounding agent for lubricants izi'g'eneral, as well as for other purposes.

The advantages of the compounded hydrocare bon oils of this invention are iliustratedby' the followingtest data:

Time a stick rings Used oil ms unus mg; Relative Relative Comp [min gt b 01m vs vs N c Baum cu 011 beanns 210 No.

Acid refined, S. A. E 1.0 Very low. Poor Poor 005 04.3 0.72

30, Western oil-No. 1. 011 No. 1 plus 0.06% 00 3.0 ...do Excellent Good 1. m 79. 7 5.54 Made with aluminum metal ailumilxum di(cetyl and cetyl phenol.

ena e OBNoJ ius1%barium' 45+ 1.5+ Low Good.... Fair 1.045 67. i 0.00- Made by reaction with cetyl p enate. bxium hydroxide. 01] No. 1 plus 1.1% cai 00+ 3.0+ Very low Excellent Very good i, 490 76. 7 3.87 Made with calcium metal eium cetyl pheuats. and cetyl phenbi. 0i1iNo llushl.0%wca1' 5.5+ do Perfect ...do.. 1, 915 85.2 3.96 Check run on above.

e um y p ena Oil No 1 plus .88% call35+ 4.5+ ...do.'..... do..... Good... 1,576 70.7 3% Made irom calcium carbide oium cetyl phenate. and cstyl phenol. Oil No. 1 plus 0.5% 0111- 121+ 4.0+ Low Verygood. Fair.-. 1.764 54.1 3.54 ads hum calcium metal cium cetyl phenate. and cstyl phenol. oicliNo. 1 1lll %96%8lm 4.0 Medium ...do Good-... 0 1, 480 57.0 3.45 0st 1 P1101311: made by sluum ee p one 7 nm thod. s. t. NE. :30, W s gi 45+ 1. 5+ Fair Poor 1.000 0&7 1.42 T me o o. pus cstsoncompomidingogon calcium cetyl phenate. in diiicrent oil. oilNmzltfllllsmill- 105 3.5 Verylow Good.-." Verygood 1.000 70.0 1.85

e um ce y p Oil No. 1 plus 1 0 cal- G) 2.0 .-.do ...do. Fair 1,250 72.5 2.00 Made with calcium metal cium di-amyl p enatc. d di-amyl hcnol. Oil No. 1 plus 1% cal- 00+ 2 H1811 -.-d0 1,425 76.7 3.01 do with um ms "t?" "mm" and "mm" phenol. 8 011 No. 2 plus 1.55% cal- 121+ 4.0+ Medium Excellent Good- 1, 107 72. 2 0.81 Made with calcium metal cinm lauryl p enate. and lanryl phenol. Oil No. 1 plus 1% cal- 45 1.5 VcrylowL I'air Fair 1,150 0.2 1.87 Made with calcium metal cigm p-tertiary amyi and MM amyl phenol. OHNo. 1 plus 0.25% cal- 20 Medium.. ...do Poor 742 57.0 8.8

cium mono-chloroamyl phenate.

1 Corrosion data not from engi e 'Ratiooitimerequirodtostick tat. ringswith compounded oil as compared with uneompoundad mineral oil.

In the above piston ring sticking tests, a single cylinder 2%" bore, 2%" stroke, Lauson gasoline engine was operated under extremely severe conditions for the purpose of developing fully piston ring sticking and piston gumming tendencies under circumstances simulating severe operating conditions encountered in the field. Operation of the motor during testswas continuous at 1600 R. P. M. except for periodic shut-downs at fliteen hour intervals for inspection; the Jacket temperature was maintained at 345 F. and sump oil temperature at 220 F. The corrosion data given, except where noted otherwise, were determined by measuring the loss of weight of metal from the bearings during runs with this type of engine under the above'severe conditions.

The metal phenates of this invention may be, added to mineral oils containing other comchlorinated phenols have been referred to and described merely to illustrate the general group of polyvalent metal salts of halogenated phenols. The other metal phenates herein disclosed may be halogenated and utilized according to the teachings of the present invention. In the halogenated compounds the chlorine or halogen atom may be present either in the aryl portion of the molecule, that is, in the benzene ring to which the metal is attached through an oxygen atom, or the halogen atom may be contained in the substituent of hydrocarbon structure attached to said benzene ring. Further, the halogen atom may be substituted in both places, that is, directly in the ring and in the substituent of hydrocarbon structure.

group having more 8. A lubricating composition comprising a hy-- drocarbon oil and by weight based containing a-halogenated phenolic. radical having more than ten carbon atoms. 7

2. A composition as defined in claim 1 in which the phenate is an alkaline earth metal phenate.

3. A composition as defined in claim 1 in which the phenate is a calcium phenate.

4. A lubricating composition comprising a. hydrocarbon oil and more than approximately 0.1% by weight based on the oil of a metal phenate containing a monmiuciear phenolic radical, said phenolic radical containing chlorine and an alkylgroup having more than four carbon atoms.

5. A lubricatingv composition comprising a hydrocarbon oil and more than approximately 0.1% by'weight based on the oil of a metal phenate containing a mononuclear phenolic radical, said phenolic radical containing a halogenated alkyl group having more than four carbon atoms.

6. A lubricating composition comprising a hydrocarbon oil and more than approximately 0.1% by weight based on the oil of an alkaline earth metal phenate containing a mononuclear phe nolic radical, said phenolic radical containing a halogenated alkyl group having more than four carbon atoms. g

7. A lubricating composition comprising a hydrocarbon oil and more than approximately 0.1% by weight based on the oil of a calcium phenate containing a mononuclear phenolic radical; said phenolic radical containing a halogenated alkyl than four carbon atoms.

drocarbon oil and more than approximately 0.1% by weight based on the oil or a metal phenate containing a phenolic radical having more than ten carbon atoms. and halogenated in the aryl portion thereof.

9. A lubricating composition comprising a hydrocarbon oil and more than approximately 0.1%

While the character of the invention has been I described in detail and numerous examples of the preparation and application of the compositiorr given, this has been done by way of illustration only and with the intention that no limitation should be imposed on the. invention thereby. It will be apparent to those skilled in the art that numerous modifications and variations of the illustrative examples may be eifected in the practice of the invention which is of the scope of the claims appended hereto.

We claim: 1. A composition of matter comprisinga byby weight based on the oil of an alkaline earth metal phenate containing a phenolic radical having more than ten carbon atoms and halogenated in the aryl portion thereof.

10. A lubricating composition comprising a hydrocarbon oil and more than approximately 0.1% by weight based on the oil of a calcium phenate containing a phenolic radical having more than ten carbon atoms and halogenated in the aryl portion thereof.

11. A compounded lubricant comprising a hydrocarbon oil and from approximately 0.1% to approximately 2% by weight based on the oil of a polyvalent metal phenate containing a halogenated phenolic radical having more than ten carbon'atoms.

ELMSLIE w. cmnpnsrza. GEORGE n. nnmson, .m. 

